Extreme pressure lubricant



' tive, diesel and aircraft engines.

Patented June 10, 1952 UNITED srrss EXTREME PRESSURE LUBRICANT poration of Delaware No Drawing. Application February 21, 1949, Serial No. 77,691

21 Claims. 1

This invention relates to a novel class of reaction products, particularly adapted to improve the properties of liquids and/or solids which are suitable for use as lubricants, coolants, rust and/or corrosion inhibiting compositions, coating compositions, and the like. More particularly, this invention pertains to lubricants such as natural or synthetic lubricants, emulsions, aqueous solutions, and organic and/or inorganic materials which can be adapted for lubricating purposes, which lubricants possess improved characteristics due to the addition thereto of a .novel multifunctional reaction product capable of imparting extreme pressure, anti-wear and anti-fouling properties, as well as acting as an inhibitor of oxidation and corrosion.

It is well known that various lubricants, whether doped or undoped, tend to oxidize and to form corrosive bodies and sludge when used in modern engines and machines operating under ordinary conditions or at high speeds, low or elevated temperatures, heavy loads and/or other adverse conditions. Some of the deterioration products of lubricants formed during their use are hard carbonaceous materials which adhere to metal surfaces and cause scratching and scufiing of movable metal parts, as well as sticking of valves and piston rings in engines. In addition, most of the presently known lubricants are generally incapable of maintaining a continuous lubricating film between movable parts, which results in a gradual or rapid wearing away of metal parts. The damage thus caused requires replacement of such parts or even the complete overhauling of engines and machines, resulting I in expensive loss of production and time.

are generally highly susceptible to oxidation and deterioration, becoming progressively more corrosive in engines and machines even under ordinary operating conditions.

To improve the lubricating properties of oils and synthetic lubricants ,it has become the practice to blend with various lubricants one, and

in most cases more than one, addition agent,

which additive has the effect or property of inhibiting deterioration of lubricants and imparting to them certain beneficial properties. Thus,

additives have been specifically designed which have the property of inhibiting corrosion of alloyed bearings, such as copper-lead, cadmiumsilver and like bearings developed for automo- Acidic oxidation or decomposition components formed in lubricants during use readily attack these bearings, but are inhibited or prevented from doing this by the formation of a corrosion protective film formed on the bearing surface with the aid of the additive. Additives have also been developed which possess the property of modifying the carbonaceous materials formed by deterioration of lubricants on piston rods, rings, valves and other metal parts in internal combustion engines, automotive and truck engines, aviation engines, high speed diesel engines and the like. Such additives serve a very important function because, by modifying this carbonaceous material so that it can be removed easily, the tendency of engine parts to become stuck is prevented or at least decreased so that ring sticking, piston scuffing, scratching and wearing away of engine parts are prevented or materially inhibited.

Other additives have been developed for the purpose of acting as detergents in lubricants in order toassist in the removal of soot, sludge, varnish or lacquer formed from deterioration of the oil when subjected to high operating temperatures. Detergents due to their cleaning action prevent the build-up of these deleterious materials and assist in removing those formed. Anti-wear additives have the property of reducing friction of movable parts or different metals. Due to the function exerted or property imparted by such additives on lubricants, wear caused by direct frictional contact of metals can be greatly reduced. Also, additives have been developed to Withstand extreme pressures, disperse impurities, solubilize certain additives and the like- The development of numerous additives has been due to the fact that most, if not all,,such additives are capable of functioning in substantially only one specific manner. Very few lubricant additives have the ability to improve a lubricant in more than just one respect. Thus, a good antioxidant might not be able to inhibit lacquer and varnish formation on piston rods or act as a detergent or corrosion inhibitor. In many cases it is found that an additive possesses'very good properties in one respect, but is the'cause of harmful formations and therefore detrimental as an additive in another respect. Therefore, other additives are frequently required to obtain a good stable lubricant. The combination of additives in lubricants wherein each additive exerts its influence without interfering with the function of other aditives is a difficult matter to attain. In most cases additives co-react or interfere with each other. To prevent this, great care must be taken in selecting the additives, mixing them in-specific proportions and continuously invention is to add to compounded or doped lubricants a multi-functional material whereby a synergistic effect is produced, resulting in a product of accentuated and improved properties. An-

other object of this inventionis to add to oleaginous materials, organic and inorganic lubricants, mineral lubricating oils, synthetic lubricants and the like, a multi-functional material so as to" inhibit oxidation and corrosion and prevent the formation of sludge, varnish and lacquer in said lubricants even under adverse operating conditions. Still another object of this invention is to use in lubricating compositions, a multi-functional material which prevents ring sticking,

as well as the sticking of other engine parts, due to deterioration of the lubricant. Also, it is an object of this invention to use in oleaginous materials, e. g., in lubricating compositions, a multifunctional material whichinhibits wear, scufling, scratching and other damage normally caused in or to engine parts. Also, it is an object of this invention to improve the lubricating and cooling properties of base materials adapted for use in cutting, quenching, drawing and rolling operations by addition to said base materials a multifunctional material of this invention. Furthermore, it is an object of this invention to provide novel multi-functional improving and enhancing additives for lubricating bases. Other'objects of this invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, this invention consists of features which will be hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain embodiments of the invention, these being illustrative of but a few variations in which the principle of the invention may be employed.

Broadly stated, this invention is directed to a class of novel reaction products and their use in various materials, said reaction product being obtained by treating with an organic phosphite compound (as hereinbelow described) a product obtained by reacting a polyhalogenated compound of the general formula RAD, wherein R4 is a halogenated organic radical which is bonded to the halogen D, with a phosphoruscontaining compound of the general structural formula:

If; If (Formula I) R,x-1 -xn,

All X f i mx-ft-xR, R,X-I -XR, Roz-rain;

(Formula n T R1XP-XR2 (Formula III) This product is formed because the radical R3 or the metal M of the starting phosphorus-containing compound has combined with the halogen -D of the starting halogenated compound RD, and the halogenated radical R4 has become bonded to the phosphorus atom of the starting phosphorus-containing compound.

The final reaction product of this invention is obtained by treating the class of compounds defined above and represented by FormulaIII with the same or different phosphorus-containing compound as represented by Formulas. I and II. Although the exact mechanism .of this final reaction is not clearly understood, it is believed that some reaction mechanism takes place between the initial reactionproduct represented by Formula III and a phosphorus compound represented by Formulas I .or II to form a reaction product which may be represented by the general formula:

In Formula IV, the various R radicals may be saturated or unsaturated.

The final reaction product of the above reaction must contain at least one P-C group and at least one and preferably more than one halogen atom, not more than four and preferably less than two carbon atoms distant from the phosphorus atom. However,-if there "are halogens attached to the terminal carbon atom so as to form the C (DEF) group, wherein D, E and F are like or different halogens, the carbon chain may be of any length desired.

In the above formulas, Ryand R2 maybe the same or different, and are selected from the group consisting of alkyl, aryl, cyclo-alkyl, alkylaryl, alkylated cyclo-alkyl, cycloalkylated aryl, arylated cylo-alkyl, and the like. Also specific illustrative radicals which are representative examples of the generic radicals mentioned are: methyl, ethyl, butyl, amyl, octyl, stearylfallyl, oleyl; phenyl, xenyl, naphthyl, anthracyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclohexylethyl, cyclohexylamyl, cyclohexylbutyl; phenylcyclohexyl, naphthylcyclohexyl; cyclohexylphenyl, cyclohexylnaphthyl; methylcyclohexyl, amylcyclohexyl, cetylcyclohexyl; methylcyclohexylbenzyl, cyclohexylcresyl, cetylphenylcyclohexyl, methylcyclohexylamyl, phenylcyclohexyl; cresyl, xylyl, dimethylphenyl, ethylphenyl, amylphenyl, cetylphenyl, ethylnaphthyl; methoxyphenyl, ethoxyphenyl, octoxyphenyl, dichlorohexoxyphenyl, thiomethoxyphenyl, selenomethoxyphenyl, selenoethyloxyphenyl, telluromethoxyphenyl, thiolauroxyphenyl, selenolauroxyphenyl; acetylphenyl, lanoylphenyl, stearoylphenyl, stearoylethyl, lauroxylethyl; etc. w r

Specific phosphite esters which may be used '5 to form reaction products of this invention may be of any of the partial or full phosphite esters mentioned in the following U. S. Patents: 2,084,270, 2,121,611, 2,188,943, 2,191,996, 2,230,543, 2,241,243, 2,326,140, 2,365,291, 2,365, 974, 2,372,244 and 2,432,095. I

Among the most preferred phosphite esters may be: diand triethyl phosphite; diand tributyl phosphite; diand trioctyl phosphite; diand tricyclohexyl phosphite; mixed isoamyl phosphites, mixed n-butyl phosphites; diand trinaphthenyl phosphites; diand triphenyl phosphites; amyl phenoxyethyl phosphite; butylphenyl phosphite; tricresyl phosphite; and diand trithio or selleno or telluro triorgano phosphites or their mixtures. Of these esters, diand triethyl phosphite; the diand trithiophosphite; the diand 'tributyl phosphite; the diand trithiophosphite; the diand triamyl phosphite; the diand trithiophosphite; the diand thriphenyl phosphite; and the diand trithiophosphite, are particularly preferred.

When dialkyl phosphites are used, they must first be converted to the metal or amine salt (Formula II) before reaction with the polyhalogenated organic compound RAD.

Any of the above phosphorus-containing compounds may be reacted with a polyhalogenated organic compound such as are listed below so as to form an organic phosphorus compound having a 19-0 linkage, said compound having at least one and preferably more than one halogen atom, not more than four carbon atoms removed from the phosphorus atom, or if there is a C(DEF), wherein D, E and F are halogen atoms, group on the terminal carbon of the chain which attaches itself to the phosphorus atom, the halogens may be more than four carbon atoms removed from the phosphorus atom: carbon tetrachloride, chloroform, methylene chloride, carbon tetrabromide, bromoform, methylene bromide, iodoform, methylene chloroiodide, hexachloroethane, methylene fluoride, difluoroethane, diand trichloroethane, polyhalogenated fatty acids in which the halo radicals are pref erably attached in the alpha or beta position to the oarboxyl radical. Specific compounds are: dichloroacetic acid, trichloroacetic acid, trifluro acetic acid, chlorofluoroacetic acid, alpha,alphadichloropropionic acid, alpha,alpha,beta,betatetrachloropropionic acid, alpha,beta-dichloropropionic acid, alpha,alpha-dichlorobutyric acid, aIph-a,beta-dichlorobutyric acid, alpha,alpha, beta-trichlorobutyric acid, alpha,betadichloroisobutyric acid, phenyl dichloroacetic acid, dibromoacetic acid, tribromoacetic acid, alpha, alpha dichloropentanoic acid, alpha,alphadibromopentanoic acid, diiodacetic acid, triiodacetic acid, beta,beta-dibromopropionic acid, alpha,alpha-dichlorocaprylic acid, and the like, can also be used.

The reaction between the phosphorus compound and the polyhalogenated non-aromatic compounds so as to effect a P-C linkage, may be carried out by admixing the two materials in such proportion so that there is generally an excess of the halogen compound present and refluxing. The desired reaction product may be removed from the mixture-by distilling under reduced pressure.

EXAMPLE I Initial reaction product A reaction product was prepared by refluxing about 50 gm. of triethyl phosphite with about 250 cc. of dry carbon tetrachloride. A colorless solution wasiformed which was distilled under reduced pressure, to yield a colorless mobile liquid, diethyl trichloromethanephosphonate, having a boiling point of around about 121 C. at 11 mm. pressure and a n of 1.4628. The reaction proceeded as follows:

, T P o o,H,)3+o on 0 our 0 C H +C H Cl Final reaction product EXAMPLE II Initial reaction product A reaction product was prepared by refluxing for about 24 hours about 50 gms.-of tributyl phosphite with about 150 gms. of dry carbon tetrachloride. A colorless solution formed which was distilled under reduced pressure to yield a prod uct, di-n-butyl 'trichloromethanephosphonate, having a boiling point of between about 150 C. and about 155 C. at 5 mm. pressure and a n of 1.4490. The reaction proceeded as follows:

Final reaction product 'Equimolar quantities of tributyl phosphite and dibutyl trichloromethanephosphonate were heated under nitrogen in the absence of solvent at a temperature ranging from to 190 C. until the reaction was completed. The final product was a viscous liquid readily soluble in mineral and synthetic oils.

EXAMPLE III Final reaction product Equimolar quantities of the initial reaction product of Example II and tri-sec-butyl phosphite were heated under nitrogen at a temperature ranging from 100 to 200 C. until the reaction was completed. The final reaction product was a viscous liquid readily soluble in mineral and synthetic oils.

EXA PLE IV Initial reaction product A reaction product was prepared by refluxing for about 24 hours about 50 gms. of tri-sec-butyl phosphite with about gms. of dry carbon tetrachloride. A colorless solution formed which was distilled under reduced pressure to yield a product, di-sec-butyl trichloromethanephosphonate, having a boiling point of between about 150 C. and about C. at 5 mm. pressure and 1a n of 1.4490. The reaction proceededas folows:

Final reaction product Equimolar quantities of the initial reaction product of Example IV and tri-sec-butyl phosphite were reacted under nitrogen at a temperasmea -m1 I ture ranging from 100 ;C. to 200 C. .until the re- .action was .completed. The .final product was a viscous liquid readily soluble'in mineral and synthetic oils.

EXAMPLE 'V I nitial' reaction product A reaction product was prepared by refluxing for about .24 hours about 50 gms. of tri-sec-butyl phosphite with about 150 gms. of dry carbon tetrachloride. A colorless solution formed which was distilled under reduced pressure to yield a product, di-sec-butyl trichloromethane phosphonate, having a boiling point of between about 150 C. and about 155 C. at mm. pressure and a n of 1.4490. The reaction proceeded as: follows:

r ooinol+ccii OC'13P(QG4H9)2+C4H9C1 Final reaction product Equimolar quantities of the initial reaction product of Example IV and tri-n-butyl phosphite were reacted under nitrogen ata temperature ranging from 100 C. to 200 C. until the reaction was completed. The final reaction product was readily soluble in mineral and synthetic .oils.

EXAIVIPLE VI Initial reaction product About 50 gms. of tributyl phosphite were heated with about 130 gms. of 1-bromo-3-chloropropahe at a temperature of between 113 C. and 118 C. for a period of about 16 hours to produce as a reaction product, dibutyl 3-chloropr0pane-1- phosphonate. perature of about 200 C. at 2 mm. of mercury pressure, and a refractive index n of 1.4472. The reaction apparently proceeded as follows:

Final reaction product Equimolar quantities of the initial reaction product of Example VI and tributyl phosphite were reacted under nitrogen at a temperature ranging from 100 C. to 200 C. until the reaction was completed. The final reaction product was readily soluble in mineral and synthetic oils.

EXAMPLE VII Initial reaction product About 46 gms. of ethyl trichloroacetate and about 40 gms. of triethyl phosphate were heated for about five hours at a temperature of about 100 C. The somewhat dark-colored reaction product thus produced'was then distilled under a vacuum to give a water-white distillate fraction having a boiling temperature of from 108 C. to 109.5 C. at -2 mm. of mercury pressure, and a refractive index (n of 1.4505. This reaction product may be represented by the formula:

Equimolar quantities of the initial reaction product of -Example VII .and tributyl phosphite werereacted under nitrogen at a temperature ranging from 100 C. to 200 C.-until the reaction This product had a boiling tem- I ":8 was completed. Thezfinal reaction product was readily soluble in mineral and synthetic oils.

' VIII initial reaction product A mixture of sym-dichlorodiethyl ether and tributyl phosphi-te were reacted for about 16 hours at about 155 C. under substantially the same conditions as described in the previous examples. The resultantreaction yielded dibutyl 2-ch 1oroethoxy) -2-etha-ne- 1- phosphonate having a boiling point between about 145 C. and 147 C. at 0.5 mm. pressure and a n5 oi 1.4472. llhe chemical formula of this product is: r

o -pmcu oomomiro CAHQ)2 Final reaction product Equimolar quantities of the initial reaction product of Example VIII and tributyl phosphite were reacted :under nitrogen at a temperature ranging from C.. to 200 C. until-the reaction was completed. The final reaction product was React-ion product of tributyl phosphite with trichloroacetic acid treated with diethyl potassium phosphite Reaction product of tricyclohexyl phosphite with chloroform treated with diethyl potassium 'phosphite Reaction product of tricyclohexyl phosphite with carbon tetrachloride treated with diethyl potas'sium phosphite Reaction product of tricyclohexyl phosphite with trichloroacetic acid treated with diethyl potassium phosphite Reaction product of amyl phenox-yethyl lithium phosphite with carbon tetrachloride treated with diethyl potassium phosphite Reactionproduct of tricresyl phosph-ite with carbon tetrachloride treated with diethyl potassium phosphite Reaction product of triethyl trithiophosphi-te with carbon tetrachloride treated with diethyl potassium, phosphi-te Reaction product of triethyl trith-iop'hosphite with trichloroacetic acid treated with diethyl potassium phosphite Reaction product of tricyclohexyl tri-thiophosphite with carbon tetrachloride treated with diethyl potassium phosphite Reaction product of triethyl mono-selenophbsphite with carbon tetrachloride treated with diethyl potassium phosphite Reaction product of tricresyl dithiophosphite with hexachloroethane treatedwithdiethyl potassium phosphite i Reaction product of sodium diethyl dithiophosphite with bromoiorm treated with diethyl potassium phosphite Reaction product of 'triamyl monothiophosphite with carbon tetrabromide treated with diethyl potassium phosphite Reaction product of triallyl phosphite with carbon tetrachloride treated with diethyl potassium phosphite The vehicles to which reaction products of this invention may be added for purposes of improving the lubricating qualities of said vehicles or for purposes 'of producing corrosionprotective compositions and the like may be divided into several groups.

The vehicles should preferably be substantially neutral, although they may be weakly acidic or basic, preferably having dissociation constants not above about 10-**. Both polar and nonpolar vehicles may be employed. Among the former are water; alcohols, such as methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, cyclohexyl, heptyl, methyl, octyl, decyl, lauryl myristyl, cetyl, stearyl, oleyl, allyl, benzyl, etc. alcohols; polyhydric alcohols, such as ethylene glycol, propylene glycol, butylene glycol, cetene glycol, glycerol, methyl glycerol, etc. phenols and various alkyl phenols and thiophenols; ketones, such as acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl butyl ketone, dipropyl ketone, cyclohexanone, and higher ketones; keto alcohols, ethers such as diethyl ether, diisopropyl ether, diethylene dioxide, beta,beta-dichlorodiethyl ether, diphenyl oxide, chlorinated diphenyl oxide, diethylene glycol, triethylene glycol; neutral esters of carboxylic and other acids such as ethyl, propyl. butyl, amyl, octyl stearyl, oleyl, phenyL'cresyl and higher acetates, propionates, butyrates, lactates, laurates, myristates, palmitates, stearates, oleates, ricinoleates, phthalates, salicylates, carbonates; natural waxes such as carnauba wax, candelilla wax, Japan wax, jojoba oil, sperm oil; fats such as tallow, lard oil, olive oil, cottonseed oil, perilla oil, linseed oil, tung oil, soya bean oil, flaxseed oil, caster oil, etc.; as well as fractions and derivatives thereof.

Vehicles of little or no polarity comprise hydrocarbons such as liquid butanes, pentanes, hexanes, heptanes, octanes, octenes, benzene, toluene, xylene, cumene, indene, hydrindene, alkyl naphthalenes, gasoline, kerosene, fuel oil,

10" gas oil, turbine oil, motor oil, mineral spirits, aromatic solvents, lubricating oils (which may be soap thickened to form greases), petrolatum, paraffin waxes, albino asphalts, etc. Generally when petroleum oils are used it is preferable that they be purified by solvent treatment so as to remove foreign matter.

Also synthetic oils may be used as the vehicles such as polymerized olefins, copolymers of alkylene glycols and alkylene oxides; organic esters, e. g. 2-ethyl hexyl sebacate, allyl laurate, and polymers thereof; dioctyl phthalate, trioctyl phosphate, polymeric tetrahydrofuran, polyalkyl silicon polymers, and the like. Mixtures of synthetic and natural lubricants and oils can be used. In addition resinous materials such as petroleum resins, natural resins as rosin, resins formed by polymerization of drying fatty oils, phenol-formaldehyde resins, glyptal-type resins formed by esterification of polyhydric alcohols with polycarboxylic acids can be used. 9

Still another class of vehicles to which condensation products of this invention can be added are water-in-oil and oil-in-water emulsions suitable for various uses such as lubricating, cooling, rust inhibiting, and the like.

The amount of additive of this invention which can be used depends upon the vehicles to which it is added and the intended purpose to which the composition is to be subjected. Generally, the additive can be used in amounts varying from 0.01% to 20% and higher.

Compositions of this invention were evaluated as extreme pressure agents by use of the fourball extreme pressure lubricating tester similar in principle to the Boerlage apparatus described in the magazine, Engineering, volume 136, July 13, 1933. This apparatus comprises four steel balls arranged in a pyramid formation. The top ball is rotated by spindles against the three bottom balls which are clamped in a stationary ball holder. The balls are immersed in the composition to be tested. Tests were run under conditions indicated in the following table and compared with other outstanding extreme pressure compounds.

Four-ball EP lubricated tester on additives of this invention in natural and synthetic lubricants I [Fixed Conditions One minute, 1500 R. P. M. ambient temperature, steel on steel] Scar Diameter (mm.) at Various Loads (kg) Seizure Base Lubricant Additive Amount Load 40 so 200 240 260 280 300 (kg') Percent di-2-ethyl hexyl seb- Finalreaction '1 52 .53 .58 .63 .70 .70 .81. 1.03 240-260 acate containing product of 15% polymeric es- Ex. IV ter of acrylic acid and 1% of an aryl amine Do. Finalreaction l 60 .91 L 140-160 product of Ex. III Do. Initialreaction l .48 .49 2.30 W 110-120 product of Ex. II. Do. Di-sec-buty] l 41 .44 1.69 1.90 80-90 trichloronietlliante onae p 05p .39 .46 .61 40-50 reac- .33 .37 .39 .45 .49 .51 .73 .76 110-120 tionproduct of x.I Do Finalreaction 1 52 .53 58 63 .70 .70 .81 1.03 240-260 product of Ex. II

.38 .501.80 42-48 P 0 treated .42 55 .65 -85 --203 55-60 castor oil 1 Phenyl-alpha-naphthylamine.

Reaction products of this invention can be- Among the specific additives for lubricating purposes which can be used are oil-soluble detergents, which include oil-soluble salts of various bases; with detergent forming-acids. Such bases include metal as well as organic bases. Metallicbases include those of alkali metals, Ca, Mg, Cu, Sr, Ba; Zn, Cd, A1, Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic bases include;various nitrogen bases as primary, secondary, tertiary and quaternary amines.

Examples of detergent forming acid are the various fatty acids of say, lO to 30 carbon atoms, tall oil acids, rosin acids, wool fat acids, paraflin wax acids (produced by oxidation of paraffin wax)" chlorinated fatty acids, aromatic hydrox-y fatty acids, parafiin wax benzoic acids, various alkyl salicylic acids, phthalic' acid monoesters, aromatic keto acids, aromatic ether acids, diphenols as di-(alkylphenol) sulfides and disulfides, methylene bis-alkyl phenols; sul'fonic acids such as may be produced by treatment of alkyl aryl hydrocarbons or high boiling petroleum oils with sulfuric acids; sulfuric acid mono-esters; phosphoric; arsonic and antimony acid monoand diesters, including the corresponding thiophosphoric and arsonicacids and the like.

Additional detergents are the alkaline earth phosphate diesters, including the thiophosphate diester; the alkaline: earth diphenolates, specificallythe calcium and barium salts of diphenol mono and polysulfides.

Non-metallic detergents include compounds such as the phosphatides such as lacithin and cephalin, certainfatty-oils as. rapeseed oils, voltolized fatty or mineral oils and the like.

An excellent metallic detergent. for thepresent purpose isthe calcium salt of oil-soluble petroleum sulfonic acids. This may be present advantageously in the amount of about 0.025%. to 022% sulfate ash. Also alkaline metal salts of alkyl phenol-aldehyde condensation products are excellent detergents.

Antioxidants comprise several types, for example, alkyl phenol'sisuch as 2,4,6-trimethyl phenol, pentamethylphenol, 2,i-dimethyl-6tertiarybutylphenol, 2,4-dimethyl-fi-octylphenol, 2,6-ditertiary-butyl-4-methylphenol, 2,4,6. tritertiarybutylphenol and the like; benzylaminophenols; amines such as dibutyla phenylenediamina. diphenylamine, phenyl-betanaphthylamine, phenyl alpha naphthylamine, dinaphthylamine.

Corrosion inhibitors or anti-rusting compounds may also be present, such as dicarboxylic acids of 16 and more carbon atoms; alkali metal and alkaline earth salts of sulfonic acids and fatty acids, organic compounds containing an acidic radical in closeproximity to a nitril'e, nitro or nitroso group (e. g. alpha-cyanostearic acid).

Additional ingredients maycomprise oil-soluble urea or thiourea derivatives, e. g. urethanes, allophanates, carbazides, carbazones, etc, polyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols: and other high molecular weight oil-soluble compounds.

Depending upon. the additional additive used and conditions under which it is used, the amount of additive used may vary from 0.01 to 2% or higher. However, substantial improvement is obtained by using amounts ranging from 0.01 to aminophenols as 12' 0.5% in combination with reaction products or thi invention. 7

This invention is a continuation-in-.-part.of our copending application Serial. No. 26;228,' filed:May 10, l948,.now Patent No: 2,573,568:issu'ed:Oct. 30,

We claim as our invention:.

1. A, mineral lubricating oil composition comprising a mineral lubricating oilrand a, minor amount, sufiicient to impart extreme pressure properties to said mineral oil, of a reaction product. of tributyl: phosphite with dibutyl trichloromethane. phosphonate, said materials being reacted in about equimolar proportions. at a tern.- perature. of from ab0ut100 C. to 200 C.

2. Amineral lubricating oil' composition com.- prising. a mineral lubricating oil and, a minor amount, sufiicient. to impart extreme. pressure. properties to said mineral oil, of a reaction product of triethyl phosphite with diethyl trichloromethane phosphonate, said materials being reacted in about equimolar proportions. at a temperature of from about 100? C..to 200 C...

3. Alubricating oil composition consisting essentially of di-2-ethyl hexyl sebacate and a minor amount, sufi'icient to impart extreme pressure propertiesto said ester; ofv a reaction product of triethylzphophit with diethyl trichloromethane phosphonate, said materialsbeing reacted in about equimolar proportions at a=temperature of from about 100 C. to 200C.

4. A lubricating. oil composition consisting essentiallyofdi-Z-ethyl hexyl sebacate'v and a minor amount, suiiicient' to impart. extreme pressure properties to said ester, of a reactionproduct; of

tributyl phosphite with dibutyl trichloromethane. phosphonate, said materials being reacted in about equimolar-proportions at a temperature of from. about 100 C. to. 200 C.

5. A lubricating oil composition consisting essentially of an oleaginous-material and a minor amount, sufiicient to impart extreme pressure properties to said oleaginous material, of a reaction product of tributyl phosphite with. dibutyl trichloromethane phosphonate, said materials being'reacted in about equimolar proportions at a temperature of from about 100 C. to 200 C.

6. Alubricating oil composition consisting essentially ofanoIeaginous material and a minor amount, sufficient to impart extreme pressure properties to said oleaginous material, of a reaction product of triethyl phosphite with diethyl trichloromethane phosphonate, said materials being'reacted inabout equimolar proportions at a temperature of from about 100 C. to 200 C.

7 A lubricating oil composition consisting essentially of an oleaginous material having incorporated therein in an amount sufficient to impart extreme pressure properties of a reaction product obtained by retreating with an alkyl phosphite, in about equimolar proportions at a temperature of from about 100C. to 200 C., an initial reaction product of a-polychlorinated lower I aliphatic hydrocarbon with-analkyl phosphite so 13 product obtained by retreating with an alkyl phosphite, in about equimolar proportions at a temperature of from about 100 C. to 200 C., an initial reaction product of a polychlorinated lower aliphatic hydrocarbon with an alkyl phosphite so as to form at least one P-R group wherein R is an alkyl radical containing at least one chlorine atom not more than four atoms from the phosphorus atom said initial reaction being carried out at reflux temperature and the proportions of the reactants being such that the halo-compound is present in an excess amount to the phosphite.

9. A lubricating oil composition consisting essentially of an oleaginous material having incorporated therein in an amount sufficient to impart extreme pressure properties of a reaction product obtained by retreating with a hydrocarbyl phosphite, in about equimolar proportions at a temperature of from about 100 C. to 200 C., an initial reaction product of a polyhalogenated lower aliphatic hydrocarbon with a hydrocarbyl phosphite so as to form at least one P-C group containing at least one halogen atom not more than four carbon atoms from the phosphorus atom said initial reaction being carried out at reflux temperature and the proportions of the reactants being such that the halo-compound is present in an excess amount to the phosphite.

10. A lubricating oil composition consisting essentially of a neutral liquid vehicle having incorporated therein in an amount suflicient to impart extreme pressure properties of a reaction product obtained by retreating with a hydrocarbyl phosphite, in about equimolar proportions at a temperature of from about 100 C. to 200 C., an initial reaction product of a polyhalogenated lower aliphatic hydrocarbon with a hydrocarbyl phosphite so as to form at least one P-C group containing at least one halogen atom not more than four carbon atoms from the phosphorus atom said initial reaction being carried out at reflux temperature and the proportions of the reactants being such that the halo-compound is present in an excess amount to the phosphite.

11. A new reaction product obtained by reacting tributyl phosphite in about equimolar proportions at a temperature of from about 100 C. to about 200 C. with dibutyl trichloromethane phosphonate.

12. A new reaction product obtained by reacting triethyl phosphite in about equimolar pro portions at a temperature of from about 100 C. to about 200 C. with diethyl trichloromethane phosphonate.

13. A new reaction product obtained by treating with a hydrocarbyl phosphite, in about equimolar proportions at a temperature of from about 100 C. to 200 C., an initial reaction product of a polychlorinated lower aliphatic hydrocarbon with a hydrocarbyl phosphite so as to form at least one P-C group containing at least two chlorine atoms not more than four carbon atoms from the phosphorus said initial reaction being carried out at reflux temperature and the proportions of the reactants being such that the halocompound is present in an excess amount to the phosphite.

14. A new reaction product obtained by treating with a hydrocarbyl phosphite, in about equimolar proportions at a temperature of from about 100 C. to 200 C., an initial reaction product of a polyhalogenated lower aliphatic hydrocarbon compound with a hydrocarbyl phosphite so as to form at least one P-C group containing at least two halogen atoms in the molecule said initial reaction being carried out at reflux temperature 14 and the proportions of the reactants being such that the halo-compound is present in an excess amount to the phosphite.

15. A lubricating oil composition consisting essentially of an oleaginous material having incorporated therein in an amount sufiicient to impart extreme pressure properties of a reaction product obtained by reacting a trialkyl phosphite with a dialkyl trichloromethanephosphonate, said phosphite and phosphonate being reacted in about equimolar proportions at a temperatur of from about C. to 200 C.

16. A lubricating oil composition consisting essentially of an oleaginous material having incorporated theren in an amount suflicient to impart extreme pressure properties of a reaction product obtained by reacting a trialkyl phosphite with a dialkyl trichloroalkanephosphonate, said phosphite and phosphonate being reacted in about equimolar proportions at a temperature of from about 100 C. to 200 C.

17. A lubricating oil composition consisting essentially of an oleaginous material having incorporated therein in an amount suflicient in impart extreme pressure properties of a reaction product obtained by reacting an alkyl phosphite with a dialkyl trihaloalkanephosphonate, said phosphite and phosphonate being reacted in about equimolar proportions at a temparature of from about 100 C. to 200 C.

18. A lubricating oil composition consisting essentially of an oleaginous material having incorporated therein in an amount suflicient to impart extreme pressure properties of a reaction product obtained by reacting a trihydrocarbyl phosphite with a dihydrocarbyl trihaloalkanephosphonate, said phosphite and phosphonate being reacted in about equimolar proportions at a temperature of from about 100 C. to 200 C.

19. A lubricating oil composition consisting essentially of a neutral liquid vehicle having incorporated therein in an amount sufiicient to impart extreme pressure properties of a reaction product obtained by reacting a hydrocarbyl phosf phite with a hydrocarbyl trihaloalkanephosphonate, said phosphite and phosphonate being reacted in about equimolar proportions at a temperature of from about 100 C. to 200 C.

20. A lubricating oil composition consisting essentially of a neutral liquid vehicle having incorporated therein in an amount sufficient to impart extreme pressure properties of a reaction product obtained by reacting a hydrocarbyl phosphite with a hydrocarbyl polyhaloalkanephosphonate, said phosphite and phosphonate being reacted in about equimolar proportions at a temperature of from about 100 C. to 200 C.

21. A new product obtained by reacting, in about equimolar proportions and at a temperature of from about 100 C. to about 200 C., a trialkyl phosphite with a dialkyl trichloromethanephosphonate. DENHAM HARMAN.

1 ROY E. THORPE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. A MINERAL LUBRICATING OIL COMPOSITION COMPRISING A MINERAL LUBRICATING OIL AND A MINOR AMOUNT OF SUFFICIENT TO IMPAT EXTREME PRESSURE PROPERTIES TO SAID MINERAL OIL, OF A REACTION PRODUCT OF TRIBUTYL PHOSPHITE WITH DIBUTYL TRICHLOROMETHANE PHOSPHONATE, SAID MATERIALS BEING REACTED IN ABOUT EQUIMOLAR PROPORTIONS AT A TEMPERATURE OF FROM ABOUT 100* C. TO 200* C. 